CN102391528B - Method for preparing monomolecular polymer nanometer particle and metal nanometer particle composite - Google Patents
Method for preparing monomolecular polymer nanometer particle and metal nanometer particle composite Download PDFInfo
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- CN102391528B CN102391528B CN 201110208707 CN201110208707A CN102391528B CN 102391528 B CN102391528 B CN 102391528B CN 201110208707 CN201110208707 CN 201110208707 CN 201110208707 A CN201110208707 A CN 201110208707A CN 102391528 B CN102391528 B CN 102391528B
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Abstract
The invention relates to a method for preparing a monomolecular polymer nanometer particle and metal nanometer particle composite, belonging to the technical field of nanometer composites and preparation thereof. The composite provided by the invention is prepared from a monomolecular polymer nanometer particle and a metal nanometer particle, wherein the monomolecular polymer nanometer particle is prepared from a highly branched polymer through intramolecular cross-linking, and the particle size is 30-120 nanometers; and the metal nanometer particle is gold or silver nanometer particle, and the particle size is 5-20 nanometers. The product is prepared by taking the intramolecularly cross-linked highly branched polymer as a template, and meanwhile, the surface of the highly branched polymer is modified by the metal nanometer particle with single dispersion. The invention has the advantages of simple and feasible method, highly stable product, difficult agglomeration and the like and has broad application prospect in the fields of photoelectric devices, catalysis and the like.
Description
Technical field
The invention belongs to nano composite material and preparing technical field thereof, be specifically related to the preparation method of a kind of organic supramolecular polymer nano granules and inorganic metal Nanocomposites.
Technical background
The nano composite material of metal and polymkeric substance has caused the research interest that people are dense in recent years.This is because this type of nano material shows special light, electricity, magnetic, machinery and catalytic property, can also play finishing, improve the effects such as wear resistance and resistance of aging, be widely used as electron device, biochemical sensor, catalyzer and magnetic storage etc., therefore aspect new function material, show wide application prospect.The performance that the nano-hybrid material of metal and polymkeric substance has all is take the small size of metallics as the basis, yet the metallic nanoparticle subsystem has very high specific surface energy usually, and the change along with factors such as its residing environment such as temperature, pH, ionic strength, shelf-times, nanoparticle is very easy to assemble, occur in case assemble, just lose the special performance that this system has, thereby limited its application.Therefore, how to prevent that its reunion from being a focus of this architectural study.
Present a kind of effective means is to add stablizer in preparation process, makes between the metal nanoparticle to produce electrostatic repulsion forces or sterically hindered repulsive force reaches stable effect.Wherein, polymkeric substance is exactly a kind of preferably stablizer, and concrete preparation method is first that the metal ion precursor is compound with specific polymkeric substance, and these polymkeric substance all contain strong electron-donating center, thereby play the effect of template, and metal ion forms strong complexing; Then under the effect of additional reducing agent, thereby the metal ion of in-situ reducing complexing forms the nano-complex of polymkeric substance and metal.Up to now, the polymkeric substance of numerous species all successfully prepares metal nanoparticle as template.For example, patent CN 101250313 has reported preparation hydrogel microsphere and inorganic nano-particle composites method; Patent CN 1509206 has reported metal with single-size characteristic and the preparation method of polymer nanocomposite.In addition, polymer nano granules, as a kind of material of nano-scale because their little sizes, in the Nano-hybrid polymeric materials preparation, also can play template effect (
Chem. Commun.,
2006, 1536 – 1538;
J. Am. Chem. Soc. 2005,
127, 8008 – 8009).
Highly-branched polymers is the spherical branching macromole of the novel class of a class, it contains a large amount of terminal active function groups and inner cavity, and synthetic easy, can be in the range scale of a few to tens of nanometers with unit molecule as the functional structure unit, for nanometer material science provides accurate synthetic technology, and can obtain various structures, morphology and properties by the peripheral active function groups modification of polymkeric substance, prepare metal nanoparticle as template.Document
Chem. Commun., 2002, 3018-3019 adopts amphipathic modified ultra-branching polymine as template complexing and stable silver ions, generates the silver nano-grain of hydridization under the reductive action of lithium triethylborohydride.Patent CN 101225227 has reported not additional reducing agent, reacts preparation ultrabranching polyamide and metal nano compound by " single stage method " in the aqueous solution under the room temperature.Yet the prepared nano hybridization particle of these methods is to connect polymkeric substance and metallics, less stable by non covalent bond.
The another kind of selectable method for preparing the hybridized nanometer particle is to pass through covalent bonds.The hybridized nanometer particle that this method makes has the stability of height.Document
Chem. Mater. 2007,
19,Utilize the unimolecular micelle of the amphipathic modified ultra-branching polymkeric substance of self-assembly to be template among 2489 – 2494, with the micellar surface that is connected to of gold nano grain covalent linkage, the mixture of preparation unimolecular micelle and gold nano grain.But its weak point is the change of ambient conditions such as temperature, solvent, pH, concentration micella is disintegrated.So, in the preparation process of this class hybrid material, need stable polymer nano granules as template, the mode by covalent linkage to polymer beads, could obtain stable hybrid nano-material in conjunction with metallics.In addition, it also is crucial controlling metallics content and disperseing the technology of preparing of yardstick, because the parameters such as the content of metallics and dispersion yardstick have determined the final response of these materials.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of single polymer molecule nano particle and metal nanoparticle mixture, the method is simple, product is highly stable and difficult reunion.
The object of the present invention is achieved like this:
The preparation method of a kind of single polymer molecule nano particle and metal nanoparticle mixture, this mixture is comprised of single polymer molecule nano particle and metal nanoparticle, wherein, the single polymer molecule nano particle is that highly-branched polymers carries out the intramolecular crosslinking gained through different linking agents, particle diameter is 30～120 nanometers, metal nanoparticle is gold or Nano silver grain, and its particle diameter is 5～20 nanometers; The preparation of this mixture comprises following concrete steps:
(1) the single polymer molecule nano particle (by Chinese patent application: 201110190432.X preparation) of functional group is contained on the preparation surface;
(2) aqueous solution of preparation metal nanoparticle, concentration be 0.1～3 mg/mL (press document:
Langmuir 1993,
9, 2301 –, 2309 preparations);
(3) the single polymer molecule nano particle with step (1) gained is dissolved in the organic solvent, and making its concentration is 0.1～2.5 mg/mL, and the metal nanoparticle aqueous solution with this solution and step (2) gained stirs 0.5～6 h under the room temperature; The volume ratio of described single polymer molecule nanoparticles solution and the metal nanoparticle aqueous solution is 1:1～1:10;
(4) still aging 24～96 h at room temperature of the mixing solutions after step (3) is stirred separate, washs and drying, obtain the mixture of described single polymer molecule nano particle and metal nanoparticle;
Wherein: described separation is to adopt centrifugation, and centrifugal speed is 5000～7000 rev/mins, and centrifugation time is 20～60 minutes; The solvent of washing is distilled water.
Described surface functional group is a kind of in sulfydryl, amino and the pyridyl.
Described organic solvent is tetrahydrofuran (THF) or acetone.
The mixture of the present invention's preparation is comprised of single polymer molecule nano particle and metal nanoparticle, single polymer molecule nano grain surface and inside all are connected with metal nanoparticle, and the content of metal nanoparticle can be regulated and control by the number of functional groups on polymer nano granules surface; Described mixture is that wherein functional group and metal nanoparticle is formed by connecting by covalent linkage.Owing to be to be connected by covalent linkage to make it have stability highly between single polymer molecule nano particle and the metal nanoparticle.In addition, the characteristics that the mixture that the present invention makes has good dispersity and is difficult for reuniting have been brought more widely application prospect to it.
The form of gained mixture of the present invention and median size are measured by atomic force microscope, transmission electron microscope and scanning electron microscope.
Description of drawings
Fig. 1 is schema of the present invention;
Fig. 2 is transmission electron microscope (TEM) figure of the golden nanometer particle of the embodiment of the invention 1;
Fig. 3 is ultraviolet-visible (UV-vis) spectrogram of the golden nanometer particle of the embodiment of the invention 1;
Fig. 4 is the single polymer molecule nano particle of the embodiment of the invention 2 and transmission electron microscope (TEM) figure of golden nanometer particle mixture;
Fig. 5 is the single polymer molecule nano particle of the embodiment of the invention 2 and ultraviolet-visible (UV-vis) spectrogram of golden nanometer particle mixture.
Specific implementation method
Further elaborate the present invention below in conjunction with embodiment, but embodiment not limitation of the present invention.Under the spirit and scope that do not deviate from inventive concept, variation and advantage that those skilled in the art can expect all are included in the present invention.
Embodiment 1
The preparation gold nano grain
Getting content is the Tetrakis hydroxymethyl phosphonium chloride aqueous solution 24 of 80 %
μL with join in the 91 mL deionized waters after 2.0 mL deionized waters mix, then adding concentration is the NaOH aqueous solution 3.0 mL of 1.0 mol/L, stirs that to add content fast after 5 minutes be 1 wt % HAuCl
4The aqueous solution 4.0 mL, solution colour becomes dark-brown gradually.Concentrating under reduced pressure is to 2/3 of original volume, with 0.2 after stirring 2 h under the room temperature
μThe membrane filtration in m standard aperture namely obtains the transparent gold nano grain aqueous solution, and 4 ° of C ageings were used in 7 days afterwards.
The TEM figure of this gold nano grain sees Fig. 2.TEM result is spheroidal particle, and median size is 5 nanometers.
Identify the formation of gold nano grain by the UV-Vis spectrometry.The UV-Vis spectrogram of this gold nano grain is seen Fig. 3.The absorption peak of gold nano grain appears at 520 nanometers.
Embodiment 2
The mixture of preparation single polymer molecule nano particle and golden nanometer particle
Get concentration and be 0.5 mg/mL particle diameter and be 40 nanometers, surface with tetrahydrofuran solution 2 mL of the single polymer molecule nano particle of mercapto functional group in 25 mL reaction flasks, the gold nano grain aqueous solution that adds preparation among the 5 mL embodiment 1 under the condition that stirs makes that the volume ratio of single polymer molecule nano particle and gold nano grain is 1:2.5 in the mixed solution.Lucifuge stirs 4 h under the room temperature, then centrifugation, and 6000 rev/mins of rotating speeds, the product deionized water wash of precipitation, repeated washing four times, drying obtains the mixture of single polymer molecule nano particle and golden nanometer particle.
The TEM figure of this nano-complex sees Fig. 4.TEM result is that spherical single polymer molecule nano grain surface and inside have more monodispersed gold nano grain, and the single polymer molecule nano particle diameter is 42 nanometers, and the gold nano grain median size is 5 nanometers.
Identify the formation of nano-complex by the UV-Vis spectrometry.The UV-Vis spectrogram of this nano-complex is seen Fig. 5.The absorption peak of single polymer molecule nano particle and gold nano grain appears at respectively 275 and 526 nanometers.
Embodiment 3
Get concentration and be 1.0 mg/mL particle diameters and be 40 nanometers, surface with tetrahydrofuran solution 2 mL of the unit molecule nano particle of mercapto functional group in 25 mL reaction flasks, other reaction conditionss in the present embodiment, step are identical with embodiment 2.The TEM detected result of the nano-complex that obtains is that unit molecule hybridized nanometer particle is less, and take the reunion of hybridized nanometer particle as main, size is in 120～270 nanometers.UV-Vis spectral detection result is that the absorption peak of single polymer molecule nano particle and gold nano grain appears at respectively 275 and 525 nanometers.
Embodiment 4
Get concentration and be 0.5 mg/mL particle diameter and be 80 nanometers, surface with tetrahydrofuran solution 2 mL of the single polymer molecule nano particle of mercapto functional group in 25 mL reaction flasks, other reaction conditionss in the present embodiment, step are identical with embodiment 2.The TEM result of the nano-complex that obtains is that spherical single polymer molecule nano grain surface and inside have monodispersed gold nano grain, and the single polymer molecule nano particle diameter is 78 nanometers, and the gold nano grain median size is 5 nanometers.UV-Vis spectral detection result is that the absorption peak of single polymer molecule nano particle and gold nano grain appears at respectively 275 and 526 nanometers.
Embodiment 5
Get concentration and be 0.5 mg/mL particle diameter and be 40 nanometers, surface with tetrahydrofuran solution 2 mL of the single polymer molecule nano particle of pyridine functional groups in 25 mL reaction flasks, adding concentration is 10 mg/mL HAuCl
4Acidic aqueous solution 5 mL (pH=2), fast adding excessive concentration behind stirring at room 24 h is the NaBH of 10 mg/mL
4The aqueous solution 5 mL continue lucifuge and stir 24 h.Other aftertreatments are identical with embodiment 2 in the present embodiment.The TEM result of the nano-complex that obtains is that spherical single polymer molecule nano grain surface and inside have monodispersed gold nano grain, and the single polymer molecule nano particle diameter is 42 nanometers, and the gold nano grain median size is 5 nanometers.UV-Vis spectral detection result is that the absorption peak of single polymer molecule nano particle and gold nano grain appears at respectively 275 and 522 nanometers.
Embodiment 6
The preparation silver nano-grain
Take by weighing 3 g glucose and 1 g polyvinylpyrrolidone, be mixed with 100 mL mixed aqueous solutions, utilize sodium hydroxide solution to regulate its pH value to 11; Take by weighing 2 g Silver Nitrates and be mixed with the 30 mL aqueous solution.In thermostat water bath, mentioned solution is heated to 70 ℃, equably be added drop-wise in mixed aqueous solution with 30 droplets/minute speed silver nitrate solution, stir 2 h and obtain black suspension, concentrating under reduced pressure is to 2/3 of original volume, with this suspension liquid centrifugation, 6000 rev/mins of rotating speeds, gained solid precipitation are scattered in the deionized water after respectively washing four times with deionized water and dehydrated alcohol.TEM result is spheroidal particle, and median size is 8 nanometers.UV-Vis spectral detection result is that the absorption peak of silver nano-grain appears at 398 nanometers.
Embodiment 7
The mixture of preparation single polymer molecule nano particle and Nano silver grain
Get concentration and be 0.5 mg/mL particle diameter and be 40 nanometers, surface with tetrahydrofuran solution 2 mL of the single polymer molecule nano particle of mercapto functional group in 25 mL reaction flasks, the silver nano-grain aqueous solution that adds preparation among the 5 mL embodiment 6 under the condition that stirs makes that the volume ratio of single polymer molecule nano particle and gold nano grain is 1:2.5 in the mixed solution.Lucifuge stirs 4 h under the room temperature, then centrifugation, and 6000 rev/mins of rotating speeds, the product deionized water wash of precipitation, repeated washing four times, drying obtains the mixture of single polymer molecule nano particle and silver nano-grain.The TEM detected result of the nano-complex that obtains is that spherical single polymer molecule nano grain surface and inside have monodispersed silver nano-grain, and the single polymer molecule nano particle diameter is 42 nanometers, and the silver nano-grain median size is 8 nanometers.UV-Vis spectral detection result is that the absorption peak of single polymer molecule nano particle and gold nano grain appears at respectively 275 and 402 nanometers.
Embodiment 8
Get concentration and be 0.5 mg/mL particle diameter and be 40 nanometers, surface with tetrahydrofuran solution 2 mL of the single polymer molecule nano particle of amido functional group in 25 mL reaction flasks, adding 5 mL concentration under the condition of stirring is the AgNO of 0.024 mol/L
3The aqueous solution.Lucifuge stirs 20 min under the room temperature, adds fast the NaBH that concentration is 10 mg/mL
4The aqueous solution 5 mL continue to stir 4 h.Other aftertreatments are identical with embodiment 7 in the present embodiment.The TEM detected result of the nano-complex that obtains is that spherical single polymer molecule nano grain surface and inside have monodispersed silver nano-grain, and the single polymer molecule nano particle diameter is 42 nanometers, and the silver nano-grain median size is 8 nanometers.UV-Vis spectral detection result is that the absorption peak of single polymer molecule nano particle and gold nano grain appears at respectively 275 and 399 nanometers.
Claims (3)
1. the preparation method of a single polymer molecule nano particle and metal nanoparticle mixture, it is characterized in that this mixture is comprised of single polymer molecule nano particle and metal nanoparticle, wherein, the single polymer molecule nano particle is that highly-branched polymers carries out the intramolecular crosslinking gained through different linking agents, particle diameter is 30～120 nanometers, metal nanoparticle is gold or Nano silver grain, and its particle diameter is 5～20 nanometers; The preparation of this mixture comprises following concrete steps:
(1) the single polymer molecule nano particle of functional group is contained on the preparation surface;
(2) aqueous solution of preparation metal nanoparticle, concentration is 0.1～3 mg/mL;
(3) the single polymer molecule nano particle with step (1) gained is dissolved in the organic solvent, and making its concentration is 0.1～2.5 mg/mL, and the metal nanoparticle aqueous solution with this solution and step (2) gained stirs 0.5～6 h under the room temperature; The volume ratio of described single polymer molecule nanoparticles solution and the metal nanoparticle aqueous solution is 1:1～1:10;
(4) still aging 24～96 h at room temperature of the mixing solutions after step (3) is stirred separate, washs and drying, obtain the mixture of described single polymer molecule nano particle and metal nanoparticle; Wherein: described separation is to adopt centrifugation, and centrifugal speed is 5000～7000 rev/mins, and centrifugation time is 20～60 minutes; The solvent of washing is distilled water.
2. preparation method according to claim 1 is characterized in that described surface functional group is a kind of in sulfydryl, amino and the pyridyl.
3. preparation method according to claim 1 is characterized in that described organic solvent is tetrahydrofuran (THF) or acetone.
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Non-Patent Citations (2)
| Title |
|---|
| "Dendrimer-Entrapped Gold Nanoparticles as a Platform";Xiangyang Shi et.al;《Small》;20070702;第3卷(第7期);全文 * |
| Xiangyang Shi et.al."Dendrimer-Entrapped Gold Nanoparticles as a Platform".《Small》.2007,第3卷(第7期), |
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